CN1476450A - Method for preparing catalyst system and its use in polymerization process - Google Patents

Method for preparing catalyst system and its use in polymerization process Download PDF

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CN1476450A
CN1476450A CNA018193986A CN01819398A CN1476450A CN 1476450 A CN1476450 A CN 1476450A CN A018193986 A CNA018193986 A CN A018193986A CN 01819398 A CN01819398 A CN 01819398A CN 1476450 A CN1476450 A CN 1476450A
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load
activator
catalyst system
bulky ligand
metallic compound
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CN1247618C (en
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ˮ�ɺ�
高珊爵
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Univation Technologies LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65904—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with another component of C08F4/64
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/902—Monomer polymerized in bulk in presence of transition metal containing catalyst
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Catalysts (AREA)

Abstract

The present invention relates to a supported catalyst composition and a method for making the supported catalyst composition and its use in a process for polymerizing olefin(s). In particular, the invention is directed to a method for making a supported catalyst composition by contacting a supported activator with a bulky ligand and a metal compound.

Description

The preparation method of catalyst system and its purposes in polymerization process
The present invention relates to prepare method and its purposes in the olefin polymerization method of catalyst system.Especially, the present invention relates to prepare the method for the catalyst composition of load activator and metallic compound and bulky ligand.
Polymerization and catalytic progress have caused producing the ability with the many novel polymers that improve physics and chemical property, and this polymkeric substance is used for the product and the application of various excellences.Along with the exploitation of raw catalyst, greatly expanded selection to the polymeric type (solution, slurry, high pressure or gas phase) that is used to produce particular polymers.Equally, the progress of polymerization technique provides more effective, high yield and economic enhanced method.What these progress specified is the technological development of adopting the bulky ligand metallocene catalyst system.Especially, typically in the slurry or gas phase process of working load catalyst system, the various different methods that are used for load bulky ligand metallocene catalyst system have been described in the art therein.
The illustrative method of production load bulky ligand metallocene catalyst system comprises: U.S. patent Nos.5, and 332,706 and 5,473,028 has taked to form by initial dipping the particular technology of catalyzer; U.S. patent Nos.5,427,991 and 5,643,847 have described the chemical bonding of non-coordination anion activator to carrier; U.S. patent No.5,492,975 have discussed the metallocene catalyst system of polymkeric substance combination; The open WO97/06186 of disclosed PCT on February 20th, 1997 has instructed and has removed inorganic and organic impurity after metalloscene catalyst self forms; The open WO97/15602 of disclosed PCT on May 1st, 1997 has discussed the metal complexes of easy load; U.S. patent No.4,937,217 have described trimethyl aluminium and the triethyl aluminum mixture that joins in the dehydrated silica not prevailingly, add metalloscene catalyst then; EP-B1-0 308 177 has described prevailingly to comprising metallocenes, trialkylaluminium and do not add moist monomer in the reactor of dehydrated silica; U.S. patent Nos.4,912,075,4,935,397 and 4,937,301 relate generally to add trimethyl aluminium adds metallocenes to form the exsiccant supported catalyst then to the silicon-dioxide neutralization of not dehydration; U.S. patent No.4,914,253 have described the adding trimethyl aluminium in dehydrated silica not, and the hydrogen desiccation catalyzer that adds metallocenes and adopt some amount then is with the production polyethylene wax; U.S. patent Nos.5,008,228,5,086,025 and 5,147,949 have described prevailingly by add trimethyl aluminium in the silicon-dioxide of water retting and form aikyiaiurnirsoxan beta and add metallocenes then with original position, formation exsiccant supported catalyst; U.S. patent Nos.4,808,561,4,897,455 and 4,701,432 have described the technology that is used to form supported catalyst, wherein with inert support, silicon-dioxide typically, calcining and contacting with activator/cocatalyst component with metallocenes; U.S. patent No.5,238,892 have described by mixed metallocene and aluminum alkyls and have added the not silicon-dioxide of dehydration then, form the exsiccant supported catalyst; With U.S. patent No.5,240,894 relate generally to by forming metallocenes/aikyiaiurnirsoxan beta reaction soln, and the slurry that adds porous support and evaporation acquisition forms the metallocenes/alumoxane catalyst system of load to remove residual solvent from carrier.
Have many about being used for preparing the technology and its discussion of load activator in the purposes of the catalyst system of olefin polymerization.The following non-limitative example that the patent disclosure of load activator is discussed comprises: U.S. patent No.5, and 728,855 related to before hydrolysis by adopting the carbon dioxide treatment trialkylaluminium, the oligopolymer alkylaluminoxane of formation load; U.S. patent No.5,831,109 and 5,777,143 discuss the load methylaluminoxane of using non-hydrolysis process preparation; U.S. patent No.5,731,451 relate to the method for preparing the load aikyiaiurnirsoxan beta by the oxygenate that adopts the trialkylsiloxy part; U.S. patent No.5,856,255 have discussed the cocatalyst (aikyiaiurnirsoxan beta or organoboron compound) that forms load under the temperature and pressure that raises; U.S. patent No.5,739,368 have discussed the thermal treatment aikyiaiurnirsoxan beta and it have been placed on method on the carrier; EP-A-0 545 152 relates to and adds metallocenes in the aikyiaiurnirsoxan beta of load and add more methylaluminoxane; U.S. patent Nos.5,756,416 and 6,028,151 have discussed the carrier of aikyiaiurnirsoxan beta dipping and the catalyst composition of metallocenes and large volume aluminum alkyls and methylaluminoxane; EP-B1-0 662 979 has discussed the purposes of the metallocenes of the support of the catalyst that contains the silicon-dioxide that reacts with aikyiaiurnirsoxan beta; PCT WO96/16092 relates to being subjected to thermal barrier and washing to remove loose aikyiaiurnirsoxan beta of employing aikyiaiurnirsoxan beta processing; U.S. patent Nos.4,912,075,4,937,301,5,008,228,5,086,025,5,147,949,4,871,705,5,229,478,4,935,397,4,937,217,5,057,475 and PCT WO94/26793 all relate to and add metallocenes in the activator of load; U.S. patent No.5,902,766 relate to have the load activator that specific aikyiaiurnirsoxan beta distributes on silicon dioxide granules; U.S. patent No.5,468,702 relate to the activator of aging load and add metallocenes; U.S. patent No.5,968,864 have discussed the employing aikyiaiurnirsoxan beta handles solid and introduces metallocenes; EP 0 747430A1 relates to the method for using metallocenes on the methylaluminoxane of load and trimethyl aluminium; EPO 969 019A1 have discussed the purposes of metallocenes and load activator; EP-B2-0 170059 relates to the polymerization process that uses metallocenes and organo-aluminium compound, is formed with machine aluminium compound by reaction trialkylaluminium and aqueous carrier; U.S. patent No.5,212,232 discussed load aikyiaiurnirsoxan beta purposes and be used to produce the metallocenes of styrenic polymer; U.S. patent No.5,026,797 has discussed the polymerization process that uses the zirconium compounds solid ingredient and adopt the water-insoluble porous inorganic oxide of aikyiaiurnirsoxan beta preliminary treatment; U.S. patent No.5,910,463 relate to by the solid support material in conjunction with dehydration, and aikyiaiurnirsoxan beta and multifunctional organic crosslinking agent prepare the method for support of the catalyst; U.S. patent Nos.5,332,706,5,473,028,5,602,067 and 5,420,220 have discussed the method for preparing the load activator, and wherein the volume of aluminoxanes solution is less than the pore volume of solid support material; WO98/02246 has discussed the silicon-dioxide that adopts the solution-treated that comprises aluminium source and metallocenes; WO99/03580 relates to the aikyiaiurnirsoxan beta of load and the purposes of metallocenes; EP-A1-0 953 581 discloses the aikyiaiurnirsoxan beta of load and the heterogeneous catalytic system of metallocenes; U.S. patent No.5,015,749 has discussed the method for using porous organic or inorganic absorbing material to prepare many alkyl aikyiaiurnirsoxan beta; U.S. patent Nos.5,445,001 and 5,534,474 relate to the preparation method who is fixed on one or more alkylaluminoxanes on solid, the granular inert support; Relate to the preparation method who adopts the solid silica that aikyiaiurnirsoxan beta handles with EP-A1-0 819 706.Equally, purpose is to disclose the load activator of usefulness and their preparation method's following document comprises: people such as W.Kaminsky, " adopting the styrene polymerization of half sandwich coordination compound of load ", Journal of Polymer Science, 37 volumes, 2959-2968 (1999) have been described the absorption methylaluminoxane and carried out the method that metallocenes adsorbs subsequently to carriers; People such as JuntingXu, " employing loads on the sign of the isotatic polypropylene of two (1-indenyl) zirconium dichloride preparations of dimetylsilyl on the pretreated silicon-dioxide of methylaluminoxane, " European Polymer Journal35 (1999) 1289-1294 have discussed the purposes that adopts the silicon-dioxide that methylaluminoxane and metallocenes handle; People such as Stephen O ' Brien, " EXAFS of the chiral olefin polymerizing catalyst of introducing in mesoporous silicon acid esters MCM-41 analyzes " Chem.Commun.1905-1906 (1997) discloses the fixedly aikyiaiurnirsoxan beta on the modification mesoporous silica; With people such as F.Bonini, " propylene polymerization of the metallocenes/MAO catalyzer by load: dynamic analysis and modeling " Journal of Polymer Science, 33 volumes, 2393-2402 (1995) have been discussed silicon-dioxide and the metallocenes that uses the methylaluminoxane load.
Although described all these methods in the art, find to need the improving one's methods of bulky ligand metalloscene catalyst of preparation load.
The invention provides new and method improved load bulky ligand metallocene catalyst system of preparation and its purposes in polymerization process.
In one embodiment, the present invention relates to a kind of preparation method of load catalyst system, comprise the steps: that (a) forms the activator of load; (b) introduce bulky ligand; With the introducing metallic compound.
On the other hand, the present invention relates to a kind of preparation method of load catalyst system, comprise the steps: that (a) is in conjunction with solid support material and activator; (b) add bulky ligand; (c) add metallic compound.In this embodiment, preferably step (b) and (c) before completing steps (a) to form the activator of load.
In another embodiment, the present invention relates to adopt load catalyst system, particularly the method for olefin polymerization in gas phase or slurry phase technology by method for preparing.
In one embodiment, the present invention relates to the method for olefin polymerization in the presence of catalyst system, this catalyst system comprises the activator of load, the binding substances of bulky ligand and metallic compound.In this embodiment, preferably before their are introduced polymerization reactor, the activator of load is combined with bulky ligand and metallic compound.
In another embodiment still, the present invention relates in reactor, the method for olefin polymerization in the presence of catalyst system, catalyst system comprises activator, solid support material, bulky ligand and metallic compound.Preferably in this embodiment, at first in conjunction with activator and solid support material to form the activator of load.
The present invention relates to prepare method with the catalyst system of working load.Be surprisingly found out that the activator of contact load and bulky ligand and metallic compound have caused active polymerizing catalyst.Although do not wish to be bound by any particular theory, believe that in the presence of the activator of load bulky ligand and metallic compound cooperate, or " self-assembly " become active olefin polymerization catalysis.Yet for the purpose of patent specification and claims, bulky ligand and metallic compound are independent components and are not equal to preformed bulky ligand metallocenes one type compound.Method of the present invention provides the catalyst system of production load and does not need to synthesize, for example, and the simple approach of bulky ligand metallocene catalyst compound.In addition, the invention provides easy change bulky ligand and do not need the handiness of synthetic another kind of bulky ligand metal types catalyst compound.This ability has many advantages, comprises the blended catalyst technology, particularly wherein adopts two or more bulky ligand metallocenes-type catalyst.
Bulky ligand of the present invention is generally open by one or more, ill-mannered, or condensed ring or member ring systems or it is in conjunction with expression.The ring of preferred suitable bulky ligand or member ring systems are typically formed by being selected from following atom: periodic table of elements 13-16 family's atom and more preferably be selected from carbon, nitrogen, oxygen, silicon, sulphur, phosphorus, germanium, boron and aluminium or its bonded atom.Most preferably ring or member ring systems are made up of carbon atom, but are not limited to form those loop chain diene of bulky ligand or other similar sense precursor as sense ligand structure such as pentadiene, cyclopentadiene, indenes, pentamethyl-cyclopentadiene, fluorine, fulvene, cyclooctatetraene base or imido part (imide ligand) cyclopentadienyl ligands or cyclopentadienyl types of ligands structure or other specific phase.
Atoms metal is preferably selected from periodic table of elements 3-15 family and group of the lanthanides or actinide elements.
Bulky ligand is open, and is acyclic, or condensed ring or member ring systems replace as the cyclopentadienyl ligands that do not replace or replace or cyclopentadienyl types of ligands, heteroatoms or contain heteroatomic cyclopentadienyl types of ligands (or both).The non-limitative example of bulky ligand comprises cyclopentadienyl ligands, ring penta phenanthryl part, indenyl ligands, benzindene ylidene ligands, fluorenyl ligand, octahydrofluorenyl part, cyclooctatetraene ylidene ligands, ring penta ring dodecylene part, nitrence base, Azulene part, pentalene part, phosphoryl part, pyrryl part, pyrazolyl part, carbazyl part and boron benzene part; comprise its hydrogenation variant, for example the tetrahydro indenyl part.
In one embodiment, bulky ligand is can be preferred and the metal η of following metallic compound-combine, preferably η 3-combination and η most preferably 5Any ligand structure of-bonded.
In another embodiment still, the atom and molecule amount (MW) of bulky ligand surpasses 60a.m.u., is preferably greater than 65a.m.u..
In another embodiment, bulky ligand can comprise and the one or more heteroatomss of carbon atom bonded that for example, nitrogen, silicon, boron, germanium, sulphur and phosphorus are to form opening, and is acyclic, or preferred condensed ring or member ring systems, and for example, heterocyclic pentylene Kiev helps part.Other bulky ligand includes but not limited to bulky amide, phosphide, alkoxide, aryl oxide, imide, carbolides, borollides, porphyrin, phthalocyanine, corrin and other polyazo macrocyclic material.
In one embodiment, adopt two or more bulky ligand.In this embodiment, bulky ligand can be identical or different.
Each bulky ligand can not replace or by substituent R in conjunction with replacing.The non-limitative example of substituent R comprises that one or more are selected from following group: hydrogen or linearity; branched-alkyl or alkenyl, alkynyl, cycloalkyl or aryl, acyl group, aroyl, alkoxyl group, aryloxy, aryl sulfo-, dialkyl amido, alkoxy carbonyl, aryloxycarbonyl, formamyl, alkyl or dialkyl amido formyl radical, acyloxy, acyl amino, aroylamino, straight chain, branching or cyclic alkylidene or its combination.In preferred embodiments, substituent R contains 50 non-hydrogen atoms at the most, preferred 1-30 carbon, and it also can be replaced by hydrogen or heteroatoms.The non-limitative example of alkyl substituent R comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl, comprises all their isomer, for example the tertiary butyl and sec.-propyl.Other alkyl comprises the organic quasi-metal group that methyl fluoride, fluoro ethyl, two fluoro ethyls, iodine propyl group, bromine hexyl, luorobenzyl and alkyl replace, and comprises trimethyl silyl, trimethylammonium germyl and methyl diethylsilane base; With the organic quasi-metal group that halo carbyl (halocarbyl) replaces, comprise three (trifluoromethyl) methyl-monosilane, two (difluoromethyl) silyls of methyl and brooethyl dimethyl germyl; With dibasic boron group, for example comprise dimethyl boron; With dibasic pnicogen group, comprise dimethyl amine, dimethyl phosphine, diphenylamine, aminomethyl phenyl phosphine, the chalcogen group comprises methoxyl group, oxyethyl group, propoxy-, phenoxy group, methyl sulfide and thioethyl ether.Non-hydrogen substituent R comprises atoms carbon, silicon, boron, aluminium, nitrogen, phosphorus, oxygen, tin, sulphur and germanium, comprise alkene as but be not limited to the unsaturated substituting group of olefinic, comprise the part of ethenyl blocking, for example fourth-3-thiazolinyl, third-2-thiazolinyl and oneself-5-thiazolinyl.Equally, at least two R groups, preferred two adjacent R groups are in conjunction with contain 3-30 ring structure that is selected from following atom with formation: carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminium, boron or its combination.Equally, substituent R group such as 1-butyl can form carbon σ key to metal M.
In another embodiment, two or more bulky ligand can be passed through bridge joint group bridge joint each other.The non-limitative example of bridge joint group comprises the bridge joint group that contains at least one 13-16 family atom, be commonly referred to divalent moiety as but be not limited to following at least one: carbon, oxygen, nitrogen, silicon, boron, germanium and tin atom or its combination.Preferred bridge joint group comprises carbon, silicon or germanium atom, most preferably at least one Siliciumatom or at least one carbon atom.The bridge joint group also can comprise the substituent R that comprises halogen as defined above.The non-limitative example of bridge joint group can be by R ' 2C, R ' 2Si, R ' 2SiR ' 2Si, R ' 2Ge, R ' P represent, wherein R ' is independently, following group: the chalcogen or the halogen of the organic quasi-metal that the organic quasi-metal that the halo carbyl of hydrogen, alkyl, substituted hydrocarbon radical, halo carbyl, replacement, alkyl replace, halo carbyl replace, dibasic boron, dibasic pnicogen, replacement.
Metallic compound of the present invention is transistion metal compound preferably, and wherein metal is selected from 4-12 family, the preferred the 4th, 5 and 6 families, and more preferably transition metal is from the 4th family, most preferably titanium, zirconium or hafnium.In another embodiment, metallic compound of the present invention is a transistion metal compound, wherein metal selected among zirconium, titanium, hafnium, chromium and vanadium.
Other part can be bonded on the metal, for example, single anion ligand, its σ is bonded on the metal.Bonding or the non-limitative example that is coupled to the part on the metal comprise weak base such as amine, phosphine, ether, carboxylicesters, diolefine, contain alkyl, hydrogen or halogen or its combination of 1-50 carbon atom.In another embodiment, be bonded to the part that two or more these parts on the metal form condensed ring or member ring systems.Other example that is bonded to the part on the metal comprises those substituting groups and comprise cyclobutyl, cyclohexyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylene radical (methylidene), methoxyl group, oxyethyl group, propoxy-, phenoxy group, two (N-methyl-anilides), dimethylformamide and dimethyl phosphide group as defined above for R.
Other bulky ligand and metallic compound are described in U.S. patent Nos.5,064,802,5,145,819,5,149,819,5,243,001,5,239,022,5,276,208,5,296,434,5,321,106,5,329,031,5,304,614,5,677,401,5,723,398,5,753,578,5,854,363,5,856,547,5,858,903,5,859,158 and 5,900,517 and the open WO93/08221 of PCT, WO93/08199, WO95/07140, WO98/11144, WO98/41530, WO98/41529, WO98/46650, WO99/02540, WO99/14221, the open EP-A-0 578 838 in WO00/35973 and WO00/35928 and Europe, EP-A-0 638 595, EP-B-0 513 380, EP-A1-0 816 372, EP-A2-0 839 834, EP-B1-0 632 819, EP-B1-0748 821 and EP-B1-0 757 996.
Same bulky ligand and metallic compound further are discussed at the open WO92/00333 of PCT, WO94/07928, WO91/04257, WO94/03506, WO96/00244, WO97/15602, WO96/33202, WO96/34021, WO97/17379, WO98/22486, WO99/20637 and WO00/11006 (metalloid salt catalyst) and U.S. patent Nos.5,057,475,5,096,867,5,055,438,5,198,401,5,227,440,5,637,660,5,539,124,5,554,775,5,756,611,5,233,049,5,744,417,5,856,258,5,264,405,6,066,704,6,069,237 (open pentadienyl parts), 6,072,067 (by the bulky ligand of heteroatoms replacement), 6,087,515 and 6,090,739 and open EP-A-0420 436 in Europe and EP-A1-0 874 005.
In another embodiment, bulky ligand comprises those bitooth ligands that contain pyridine or quinoline moiety, as the U.S. application No.09/103 that submits on June 23rd, 1998,620 (now are issued as US patent No.6,103,657) those that describe in, or those bulky ligand of in open WO99/01481 of PCT and WO98/42664, describing.
Within the scope of the present invention be that in one embodiment, bulky ligand and metallic compound are included in the Ni that describes in the following document 2+And pd 2+Those title complexs: people such as article Johnson, " be used for the new Pd (II) of ethene and alpha-olefine polymerizing-and Ni (II) is catalyst based ", J.Am.Chem.Soc.1995,117, people such as 6414-6415 and Johnson, " by the ethene of Pd (II) catalyzer and the copolymerization of propylene and functional vinyl monomers ", J.Am.Chem.Soc.1996,118,267-268 and on August 1st, 1996 disclosed WO96/23010, WO99/02472, U.S. patent Nos.5,852,145,5,866,663 and 5,880,241.
That be included as bulky ligand equally is those diimine class part: PCT open WO96/23010, WO97/48735 and the people such as WO98/40374 and Gibson of disclosed 8-10 family metallic compound in following document, Chem.Comm., 849-850 page or leaf (1998).
Other bulky ligand and metallic compound are described in EP-A2-0 816 384 and U.S. patent No.5,851,945.In addition, bulky ligand comprises by people such as D.H.McConville and existing Organometallics1195,14, two (aryl amido) parts of the bridge joint of describing in the 5478-5480 page or leaf and at U.S. patent No.5, two (the hydroxyaromatic nitrogen ligand) described in 852,146.
In one embodiment, metallic compound of the present invention is represented by following general formula: ML x
Wherein M is a periodic table of elements 3-12 family, preferred 4-10 family, more preferably 4-6 family and most preferably group-4 metal and particularly zirconium, titanium or hafnium; L is identical or different and be selected from hydrogen, halogen, alkyl, alkoxide, aryl oxide, carboxylate salt, carbon diacid salt (carbodionate), acid amides, carbaminate and phosphide; " x " is the integer that depends on the metal valence state, makes that preferably metallic compound is a neutral compound, and wherein " x " equals the valence state of metal.
Non-limiting preferred metallic compound comprises: ZrCl 4, ZrBr 4, ZrI 4, Zr (CH 2C 6H 5) 4, Zr[CH 2C (CH 3) 2C 6H 5] 4, Zr[CH 2Si (CH 3) 3] 4, Zr (methyl ethyl diketone) 4, Zr (2,2,6,6-tetramethyl--3,5-heptane diacid) 4, Zr (F) 3(methyl ethyl diketone), Zr (ethanol) 4, Zr (trimethyl carbinol) 4, Zr (phenol) 4, Zr (NMe 2) 4(Me is a methyl), Zr (NEt 2) 4(Et is an ethyl), Zr (diethylamino formic acid) 4, Zr (dimethylamino formic acid) 4, Zr (PIVALIC ACID CRUDE (25)) 4, Zr (phenylformic acid) 4
For the purpose of this patent specification and claims, term " activator " is defined as any compound or component or method, and it can activate of the present invention any bulky ligand and the metal compound combination that is used for olefinic polymerization.
Non-limiting activator for example comprises Lewis acid or non-coordination ion activator or ionization activator or any other compound, comprises Lewis base, aluminum alkyls, general type promotor and binding substances thereof.Use aikyiaiurnirsoxan beta or modified alumoxane as activator within the scope of the present invention, or use neutral or anionic ionization activator, as three (normal-butyl) ammonium four (pentafluorophenyl group) boron, three perfluorophenyl boron metalloid precursors or three perfluor naphthyl boron metalloid precursors, the assorted borine negatively charged ion (WO98/43983) of many halogenations or its binding substances (or using aikyiaiurnirsoxan beta or modified alumoxane and ionization activator).
Have the whole bag of tricks of preparation aikyiaiurnirsoxan beta and modified alumoxane, their example is described in U.S. patent Nos.4,665,208,4,952,540,5,091,352,5,206,199,5,204,419,4,874,734,4,924,018,4,908,463,4,968,827,5,308,815,5,329,032,5,248,801,5,235,081,5,157,137,5,103,031,5,391,793,5,391,529,5,693,838,5,731,253,5,731,451,5,744,656,5,847,177,5,854,166,5,856,256 and the open EP-A-0 561 476 in Europe, EP-B1-0 279 586, EP-A-0 594 218 and EP-B1-0 586 665, with the open WO94/10180 of PCT.Other aikyiaiurnirsoxan beta is included in EP-B1-0 621 279 and U.S. patent No.6, siloxy-aikyiaiurnirsoxan beta of describing in 060,418 and the chemical functionalization carboxylicesters aikyiaiurnirsoxan beta of describing in WO00/09578.
Organo-aluminium compound as activator comprises trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum and tri-n-octylaluminium.
The ionization compound can comprise active proton, or associates with the residual ion of ionization compound but not coordination or only loosely be coordinated to some other positively charged ions on the residual ion of ionization compound.Such compound is described in the open EP-A-0 570 982 in Europe, EP-A-0520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 and EP-A-0 277 004, with U.S. patent Nos.5,153,157,5,198,401,5,066,741,5,206,197,5,241,025,5,384,299,5,502,124, with 6, the U.S. patent application No.08/285 that submitted on August 3rd, 078,460 and 1994,380 (are convenient to the part continuation application submitted to June 7 nineteen ninety-five number 08/474,948 abandon, now be disclosed as US patent No.5,643,847).
Other activator be included in describe among the open WO98/07515 of PCT those as three (2,2 ', 2 "-nine fluorine biphenyl) hydrofluoaluminic acid ester.The binding substances of activator is also by the present invention imagination, for example, bonded aikyiaiurnirsoxan beta and ionization activator, referring to for example, the open WO94/07928 of EP-B1-0 573 120, PCT and WO95/14044 and U.S. patent Nos.5,153,157 and 5,453,410.WO98/09996 has described employing perchlorate, periodate and iodate, comprises their hydrate activated metal compound.WO98/30602 and WO98/30603 have described the purposes of lithium (2,2 '-two phenyl-two trimethyl silicane acid esters) 4THF as activator.EP-A2-0 103 675 has described the fluorinated organic compounds activator.WO99/18135 has described the purposes of organic boron-aluminium activator.EP-B1-0 781 299 has described and has used compatible negatively charged ion bonded silyl salt with non-coordination.Other activator for example is described in, U.S. patent Nos.5,849,852,5,859,653,5,869,723 and 6,030,917 (gallium anionoid activators) and PCT WO98/32775, WO00/09513 (three kinds of coordination aluminium activators) and WO00/20115.
Any conventional carrier material can be used for the present invention.Preferred carrier materials is a porous carrier materials, for example, and talcum, inorganic oxide and butter.Other solid support material comprises resinous support material such as polystyrene, functionalized or crosslinked organic carrier, as polystyrene divinylbenzene polyolefine or polymer complex, zeolite, clay or any other organic or inorganic solid support material and composition thereof.
Preferred solid support material is an inorganic oxide, and it comprises those the 2nd, 3,4,5,13 or 14 family metal oxides.Preferred solid support material comprise silicon-dioxide, aluminum oxide, silica-alumina, magnesium chloride, and composition thereof.Other useful carrier material comprises magnesium oxide, titanium dioxide, zirconium white, montmorillonite (EP-B1 0 511 665) and hydrotalcite.Equally, can use the binding substances of these solid support materials, for example, silicon-dioxide-chromium, silica-alumina and silica-titania.
Preferred carrier materials, most preferably the surface-area of inorganic oxide is the about 700m of about 10- 2/ g, pore volume are that about 4.0cc/g of about 0.1-and mean pore size are the about 500 μ m of about 5-.More preferably, the surface-area of solid support material is the about 500m of about 50- 2/ g, pore volume are that about 3.5cc/g of about 0.5-and mean pore size are the about 200 μ m of about 10-.Most preferably the surface-area of solid support material is the about 400m of about 100- 2/ g, pore volume are that about 3.0cc/g of about 0.8-and mean pore size are the about 100 μ m of about 5-.The mean pore size of carrier of the present invention typically has the aperture of following scope: 10-1000 dust, preferably about 500 dusts of 50-and most preferably about 350 dusts of 75-.
Solid support material can chemical treatment, is for example adopting fluoride compound to handle described in the WO00/12565.
Can use one or more carrying methods well known in the art, above-mentioned activator is combined with same one or more above-mentioned solid support materials.For example, in the most preferred embodiment, activator is deposited on the solid support material, contact, or introduce in the solid support material, be evaporated on the solid support material,, cut out in the material or absorption or absorption on solid support material at carrier with the solid support material reaction with solid support material.
The activator of other load is described in for example WO00/13792, and it mentions the load boron that comprises the solid acid title complex.
In the preferred method that forms the load activator, the amount of fluid that wherein has activator is following quantity: less than the solid support material pore volume four times are more preferably less than three times, even are more preferably less than twice; Preferred range is 1.1 times of-3.5 times of scopes and most preferably is 1.2-3 times of scope.In other embodiments, the amount of fluid that wherein has activator is 1-less than 1 times the solid support material pore volume that is used to form the load activator.
The program of measuring the total pore volume of porous support is being known in the art.A kind of details of these programs is discussed at volume 1, Test method in the catalyticing research(AcademicPress, 1968) (especially referring to 67-96 page or leaf).This preferred program comprises the classical BET equipment that is used for the nitrogen absorption.Another kind of method well known in the art is described in Innes, By liquid The overall porosity of titrating fluid catalyst and particle density, 28 volumes, No.3, AnalyticalChemistry 332-334 (in March, 1956).
In one embodiment, the activator of load is the solid that is in drying regime.In another embodiment, the activator of load is in substantially dry state or slurry, preferably is in the mineral oil slurry.
In another embodiment, use two or more independent load activators, perhaps, use two or more the different activators on single carrier, combine with bulky ligand and metallic compound.
Load catalyst system of the present invention generally comprises the activator of above-mentioned load, and bulky ligand and metallic compound are with the combination of any order, and contact is evaporated, blend, bonding or mixing (or its any combination).
In an embodiment of the inventive method, before the activator of load is in joining metallic compound, combine with bulky ligand.In another embodiment, bulky ligand is at first contacted with metallic compound, and combine with the activator of load then.In other embodiments, activator and bulky ligand or metallic compound (or both) are combined forming mixture, and then mixture is joined in the solid support material.
In one embodiment, the activator with load contacts with two or more bulky ligand and one or more metallic compounds.In one embodiment, two kinds of bulky ligand are identical and use one type metallic compound.In another embodiment, with a kind of metallic compound, or two kinds of different metallic compounds are used in combination two types of differences or contain the bulky ligand of different substituents.
In another embodiment, the activator of load is 99.9wt%-50wt% to bulky ligand and metallic compound in conjunction with quantity (weight percentage), the preferred about 60wt% of about 99.8wt%-, the more preferably from about about 70wt% of 99.7wt%-and the most preferably from about about 80wt% of 99.6wt%-.
In another embodiment still, metallic compound is 0.01-100 to the mol ratio of bulky ligand, preferred 0.02-50, more preferably 0.05-20, most preferably 0.1-10.
In another embodiment still, the mol ratio of the metal of the metal to metal compound of activator is 5000-1, preferably about 2000-2, more preferably from about 1000-about 5 and most preferably from about 500-about 10.
When activator comprises aluminium, during preferred aikyiaiurnirsoxan beta, the mol ratio of the metal of the metal to metal compound of activator component is 0.3: 1-1000: 1, preferred 20: 1-800: 1 and most preferably 50: 1-500: 1.
When activator is the ionization activator as based on those of negatively charged ion four (pentafluorophenyl group) boron the time, the mol ratio of the metal component of the metal pair bulky ligand metalloscene catalyst of activator component is preferably 0.3: 1-3: 1.
In other embodiments of the present invention, when contacting with metallic compound with bulky ligand, the activator of load is in the state of drying or substantially dry, or in solution.The load catalyst system that obtains with drying or substantially dry state, or as slurry, is preferably used in mineral oil.Equally, can be before it introduce in the polymerization reactor, with dry load catalyst system of the present invention slurryization again in liquid such as mineral oil, toluene or any hydrocarbon.
In addition, the activator of imagination load, bulky ligand can be used in the identical solvent or different solvents with metallic compound.For example, bulky ligand can be in toluene, metallic compound in iso-pentane and the activator of load at mineral oil, or in the combination of any solvent.
The activator of preferred combination load, the temperature that contacts of bulky ligand and metallic compound is 0 ℃-Yue 100 ℃, more preferably 15 ℃-Yue 75 ℃, most preferably under about envrionment temperature and pressure.
Preferably, the activator and the bulky ligand of load contacted with metallic compound greater than 1 second, preferred about 1 minute-Yue 48 hours, more preferably from about 10 minutes-Yue 10 hours and most preferably from about 30 minutes-Yue 6 hours time.Only represent mixing time duration of contact.
Static inhibitor or surface-modifying agent can be used for and load activator of the present invention, bulky ligand and metallic compound combination.Referring to those reagent and the properties-correcting agent for example in the open WO96/11960 of PCT, described.Equally, apply for serial No.09/113 as the U.S. that submits on July 10th, 1998, the carboxylate salt of the metal ester of describing in 216, for example ALUMINUM CARBOXYLIC such as list, two and Aluminium Tristearate Micronized sterile, aluminium octoate, aluminium oleate and cyclohexyl butyric acid aluminium can be used for activator, bulky ligand and the metallic compound combination with load.
In one embodiment of the invention, at the activator of load, bulky ligand and metal compound combination exist down before main polymerization, pre-polyolefine, preferred C 2-C 30Alkene or alpha-olefin, optimal ethylene or propylene or its binding substances.Can gas phase, solution or slurry mutually in, comprise under high pressure intermittently or carry out pre-polymerization continuously.Pre-polymerization can be adopted any olefinic monomer or binding substances or carry out in the presence of any molecular weight regulator such as hydrogen.For the example of pre-polymerization program, referring to U.S. patent Nos.4,748,221,4,789,359,4,923,833,4,921,825,5,283,278 and 5,705,578 disclose EP-B1-0 279 863 with Europe discloses WO97/44371 as PCT.
Load catalyst system of the invention described above or composition are applicable to any polymerization process under the wide region temperature and pressure.Temperature can be-60 ℃～about 280 ℃, preferred 50 ℃-Yue 200 ℃ and the pressure that adopts can be 1 normal atmosphere-Yue 500 normal atmosphere or higher.
Polymerization process comprises solution, gas phase, slurry phase and high pressure method or its combination.The special preferably gas phase or the slurry phase polymerisation of one or more alkene, at least a of alkene is ethene or propylene.
In one embodiment, method of the present invention relates to solution, high pressure, slurry or the gas phase polymerization process of following material: contain 2-30 carbon atom, preferred 2-12 carbon atom and more preferably one or more olefinic monomers of 2-8 carbon atom.The present invention is specially adapted to the polymerization of following two or more olefinic monomers: ethene, propylene, butene-1, amylene-1,4-methyl-amylene-1, hexene-1, heptene-1, octene-1 and decylene-1.
Other monomer that is used for the inventive method comprises ethylenically unsaturated monomer, contains diolefine, conjugation or non-conjugated diene, polyenoid, vinyl monomer and the cycloolefin of 4-18 carbon atom.Be used for vinylbenzene, ethylidene norbornene, Dicyclopentadiene (DCPD) and cyclopentenes that non-limitative example of the present invention can comprise that norbornylene, norbornadiene, iso-butylene, isopentene, vinyl benzo tetramethylene, vinylbenzene, alkyl replace.
In the most preferred embodiment of the inventive method, produce the multipolymer of ethene, wherein in gas phase process polymerization with the following material of ethene: contain at least a 4-15 of a having carbon atom, preferred 4-12 the carbon atom and the comonomer of the alpha-olefin of 4-8 carbon atom most preferably.
In another embodiment of the inventive method, with ethene or the propylene comonomer polymerization different with at least two kinds, optionally a kind of comonomer can be a diolefine, to form terpolymer.
In one embodiment, the present invention relates to the polymerization process of the independent propylene of polymerization or propylene and following material, particularly gas phase or slurry phase process: comprise one or more other monomers of ethene, or contain other alkene (or both) of 4-12 carbon atom.Can use as at U.S. patent Nos.5,296,434 and 5,278,264 given bridge bulky ligand of describing and metallic compound are produced polyacrylic polymer.
Typically in gas phase polymerization process, adopt circulation continuously, wherein in part of reactor assembly round-robin,, be called cycling stream or fluidizing medium in addition, in reactor, heat by heat of polymerization with recycle gas stream.Cooling system by the reactor outside is removed this heat from the circulation composition in round-robin another part.Generally speaking, in producing the gas fluidized bed process of polymkeric substance, cross fluidized-bed and circulate continuously under reaction conditions, will comprising one or more monomeric gas communication in the presence of the catalyzer.Extract and loop back gas stream out reactor from fluidized-bed.Simultaneously, polymer product is added to replace the polymeric monomer from the reactor extraction with fresh monomer.Referring to for example U.S. patent Nos.4,543,399,4,588,790,5,028,670,5,317,036,5,352,749,5,405,922,5,436,304,5,453,471,5,462,999,5,616,661 and 5,668,228.
Reactor pressure in the gas phase process can be at following range: about 100psig (690kPa)-Yue 500psig (3448kPa), preferred about 200psig (1379kPa)-Yue 400psig (2759kPa), more preferably from about 250psig (1724kPa)-Yue 350psig (2414kPa).
Temperature of reactor in the gas phase process can be in following range: about 30 ℃-Yue 120 ℃, and preferred about 60 ℃-Yue 115 ℃, more preferably from about 70 ℃-Yue 110 ℃ and most preferably from about 70 ℃-Yue 95 ℃.
Other gas phase process by the inventive method imagination comprises series connection or multistage polymerization method.Gas phase process by the present invention's imagination is included in those that describe in the following document equally: U.S. patent Nos.5,627,242,5,665,818 and 5,677,375 and Europe open EP-A-0794 200, EP-B1-0 649 992, EP-A-0 802 202 and EP-B-0 634 421.
In preferred embodiments, the reactor of Cai Yonging is method production competent and of the present invention greater than 500 pounds of polymkeric substance (227Kg/hr)-Yue 200 per hour in the present invention, 000 pound/hr (90,900Kg/hr) or higher polymkeric substance, be preferably greater than 1000 pounds/hr (455Kg/hr), more preferably greater than 10,000 pounds/hr (4540Kg/hr), even more preferably greater than 25,000 pound/hr (11,300Kg/hr), still more preferably greater than 35,000 pounds/hr (15,900Kg/hr), still in addition more preferably greater than 50,000 pounds/hr (22,700Kg/hr) with most preferably greater than 65,000 pound/hr (29,000Kg/hr)-greater than 100,000 pounds/hr (45,500Kg/hr).
Slurry phase polymerisation process generally uses about 50 normal atmosphere of about 1-and even bigger pressure and 0 ℃-Yue 120 ℃ temperature.In slurry polymerization, in the liquid polymeric diluent medium, form the suspension of solid, granular polymer, to wherein adding ethene and comonomer and common hydrogen with catalyzer.The suspension that will comprise thinner intermittently or remove from reactor continuously wherein separates volatile constituent from polymkeric substance, and optionally after distillation, is recycled to reactor.The liquid diluent that adopts in polymerisation medium contains the alkane of 3-7 carbon atom typically, preferred branched alkane.The medium that adopts should be liquid and relative inertness under polymerizing condition.When using propane medium, technology must and be operated more than the pressure in the reaction diluent critical temperature.Preferably, adopt hexane or Trimethylmethane medium.
Preferred polymeric technology of the present invention is called the particulate forms polymerization, or slurry process, wherein temperature is remained on polymkeric substance and enters below the temperature of solution.Such technology is being known in the art, and for example is described in U.S. patent No.3,248,179.Other slurry process comprise adopt annular-pipe reactor those and with series, parallel or its in conjunction with adopting those of a plurality of stirred reactors.The non-limitative example of slurry process comprises continuous endless tube or stirred pot method.Equally, other example of slurry process is described in U.S. patent No.4,613,484.
In embodiments, the reactor that uses in slurry process of the present invention is method production competent and of the present invention greater than 2000 pounds of polymkeric substance per hour (907Kg/hr), more preferably greater than 5000 pounds/hr (2268Kg/hr) with most preferably greater than 10,000 pounds/hr (4540Kg/hr).In another embodiment, the slurry-phase reactor production of Shi Yonging in the methods of the invention is greater than 15,000 pounds of polymkeric substance per hour (6804Kg/hr), be preferably greater than 25,000 pounds/hr (11,340Kg/hr)-Yue 100,000 pounds/hr (45,500Kg/hr).
The example of solution methods is described in U.S. patent Nos.4,271,060,5,001,205,5,236,998 and 5,589,555.
The preferred method of the present invention is a method wherein, preferred slurries or gas phase process are in the presence of bulky ligand metallocene catalyst system of the present invention and do not exist or substantially without any scavenging agent, operate under the situation as triethyl aluminum, trimethyl aluminium, triisobutyl aluminium, tri-n-hexyl aluminum, diethylaluminum chloride and dibutyl zinc.This preferred method is described in open WO96/08520 of PCT and U.S. patent No.5,712,352 and 5,763,543.
The polymkeric substance of being produced by the inventive method can be used for a variety of products and end-use application.The polymkeric substance of being produced by the inventive method comprises linear low density polyethylene, elastomerics, plastomer, high density polyethylene(HDPE), new LDPE (film grade), polypropylene and polypropylene copolymer.
Polymkeric substance, typically the density of polyvinyls is 0.86g/cc-0.97g/cc, preferred 0.88g/cc-0.965g/cc, more preferably 0.900g/cc-0.96g/cc, even more preferably 0.905g/cc-0.95g/cc, still even more preferably 0.910g/cc-0.940g/cc and most preferably greater than 0.915g/cc, be preferably greater than 0.920g/cc and most preferably greater than 0.925g/cc.According to ASTM D1505 and D2839 measuring density.
The molecular weight distribution of the polymkeric substance of being produced by the inventive method, weight-average molecular weight is to number-average molecular weight (M w/ M n) typically be greater than 1.5-about 15, about 10 greater than 2-especially, more preferably greater than about 2.2-less than about 8 and 2.5-8 most preferably.
Equally, polymkeric substance of the present invention typically has by what form that Tile Width index (CDBI) measures and narrowly forms distribution.The further details of determining multipolymer CDBI is known to those skilled in the art.Referring to, for example, on February 18th, 1993 disclosed PCT patent application WO93/03093.
The polymkeric substance of bulky ligand metallocene catalyst of the present invention CDBI in one embodiment is generally greater than 50%-100%, preferred 99%, preferred 55%-85% and more preferably 60%-80%, even more preferably greater than 60%, still even more preferably greater than 65%.
In another embodiment, the CDBI that uses the polymkeric substance that bulky ligand metallocene catalyst system of the present invention produces is less than 50%, is more preferably less than 40% and most preferably less than 30%.
Melting index (MI) or (I that polymkeric substance of the present invention is measured by ASTM-D-1238-E in one embodiment 2) be 0.01dg/min-1000dg/min, the about 100dg/min of 0.01dg/min-more preferably from about, even the more preferably from about about 50dg/min of 0.1dg/min-and the most preferably from about about 10dg/min of 0.1dg/min-.
Polymkeric substance of the present invention melting index in embodiments is than (I 21/ I 2) (I 21Measure by ASTM-D-1238-F) be 10-less than 25, more preferably from about 15-is less than 25.
Polymkeric substance of the present invention melting index in preferred embodiments is than (I 21/ I 2) (I 21Measure by ASTM-D-1238-F) be preferably more than 25, more preferably greater than 30, even more preferably greater than 40, still even more preferably greater than 50 with most preferably greater than 65.In embodiments, polymkeric substance of the present invention can have that narrow molecular weight distributions and wide composition distribute or vice versa and can be by at U.S. patent No.5, those polymkeric substance of describing in 798,427.
In another embodiment still, produce acronal in the methods of the invention.These polymkeric substance comprise Atactic Polypropelene, isotatic polypropylene, half isotactic and syndiotactic polypropylene.Other propene polymer comprises propylene block or impact copolymer.The propene polymer of these types is being known in the art.Referring to, for example, U.S. patent Nos.4,794,096,3,248,455,4,376,851,5,036,034 and 5,459,117.
Can be with polymkeric substance of the present invention and any other polymer blending or coextrusion (or both).The non-limitative example of other polymkeric substance comprises linear low density polyethylene, elastomerics, plastomer, hp-ldpe, high density polyethylene(HDPE) and the polypropylene of producing by conventional Ziegler-Natta or bulky ligand metallocene catalyst (or both).
Polymkeric substance of being produced by the inventive method and blend thereof can be used for extruding shaping operation and blowing, injection moulding and rotational molding with coextrusion as film, sheet and fiber.Film comprises by coextrusion or the blowing or the casting films that are formed by lamination, and it contacts with non-food product in Food Contact and be used as shrink film, adhesive film, stretched film, sealing membrane, alignment films, fast food packing, heavy loading bag, groceries bag in using, smokes and fried food packing, medical package, industrial lining, film etc.Fiber comprise be used to weave or melt spinning, solvent spinning and the meltblown fibers operation of non-woven form with preparation strainer, diaper fabric, medical clothes, with textiles (geotextile) etc.Extruded product comprise medical pipe, electric wire and cable coating, with film and pond lining.Moulded parts comprises that form is the list and the multi-layer structure material of bottle, jar, big hollow piece, rigidity food product containers and toy etc.
Embodiment
For the of the present invention better understanding that comprises its representative advantages is provided, provide following examples.
Active numerical value is the normalized numerical value of producing according to the per hour every 100psi of every mmol transition metal (690kPa) vinyl polymerization pressure in the catalyzer of polymkeric substance gram number.MI is a melting index, and is reported to the D-1238 according to ASTM, the per 10 minutes gram numbers of condition E.FI is a flow index, and uses under 10 times of weight according to ASTM D-1238 being used for above melting index, and condition F measures.MFR is the melt flow ratio, and is FI: the ratio of MI.
MAO is the methylaluminoxane (30wt%) in the toluene, available from AlbemarleCorporation, and Baton Rogue, Louisiana.
Kaydol, slab oil, available from Witco Corporation, Memphis, Tennessee, and by at first adopting the nitrogen degassing 1 hour, then by making with extra care under vacuum, heating 10 hours under 80 ℃.
Tetrabenzyl zirconium (Zr (CH 2C 6H 5) 4) and two (indenyl) zirconium dichloride available from BoulderScientific Company.
Indenes and pentamethyl-cyclopentadiene are available from Aldrich Chemical Company. Embodiment 1 The preparation of load MAO (SMAO)
(MAO is available from Albemarle Corporation, Baton Rogue, Louisiana) toluene solution of preparation methylaluminoxane (MAO) for 30wt%MAO by mixing 960g in the toluene of 2.7 liters of dryings, the degassing.With this solution stir at ambient temperature add simultaneously 850g silica gel (Davison 955,600 ℃ of down dehydrations, available from W.R.Grace, DavisonDivision, Baltimore, Maryland).The slurry that obtains was stirred 1 hour at ambient temperature and under reduced pressure adopt nitrogen gas stream under 85 ℃, to remove solvent.Continuation drying constant 2 hours up to material temperature.The unrestricted flow white powder that obtains has the aluminium heap(ed) capacity of every gram solid 4.1mmol Al. Embodiment 2 The preparation of load tetrabenzyl zirconium (TBZ) (composition A)
In loft drier, in the 60ml bottle that is equipped with magnetic stirring bar, add the Kaydol oil of 0.050g tetrabenzyl zirconium (0.110mmol) and 19.1g drying, the degassing.The yellow slurry that obtains was stirred 2 hours at ambient temperature, add the above-mentioned SMAO of 3.43g embodiment 1 then.Then this mixture was stirred before being used for polymerization 12 hours at ambient temperature. Embodiment 3 The preparation of load indenes of the present invention (IN) and tetrabenzyl zirconium (TBZ) mixture (composition B)
In loft drier, in the 60ml bottle that is equipped with magnetic stirring bar, add 0.100g tetrabenzyl zirconium (0.220mmol), the Kaydol oil of 0.110g indenes (0.948mmol) and 38.0g drying, the degassing.The greenish orange color contamination compound that obtains was stirred 2 hours at ambient temperature, add the above-mentioned SMAO of 6.70g embodiment 1 then.Then the slurry that obtains was stirred before being used for polymerization 12 hours at ambient temperature. Embodiment 4 The present invention adopts the processing (composition C) of the load TBZ of indenes
In loft drier, the silicon dioxide carried TBZ in the Kaydol oil of embodiment 2 stirred at ambient temperature add the pure indenes of 0.043g (0.371mmol) simultaneously.The orange slurry that obtains was stirred before being used for polymerization 12 hours at ambient temperature. Embodiment 5 Load pentamethyl-cyclopentadiene (Cp of the present invention * ) and tetrabenzyl zirconium (TBZ) mixture (composition D) Preparation
In loft drier, in the 60ml bottle that is equipped with magnetic stirring bar, add 0.049g tetrabenzyl zirconium (0.108mmol), the Kaydol oil of 0.061g pentamethyl-cyclopentadiene (0.449mmol) and 18.1g drying, the degassing.This mixture was stirred 2 hours at ambient temperature, add the above-mentioned SMAO of 3.19g embodiment 1 then.The orange slurry that will obtain then stirred before being used for polymerization 12 hours at ambient temperature. Embodiment 6 Pentamethyl-cyclopentadiene (the Cp that the present invention is silicon dioxide carried * ) and tetrabenzyl zirconium (TBZ) mixture The preparation of (composition E)
According to the same program of embodiment 5, difference is to use 0.028g pentamethyl-cyclopentadiene (0.206mmol). Comparative Examples 7 The preparation of silicon dioxide carried two (indenyl) zirconium dichlorides (INZ)
In loft drier, the Kaydol oil of the INZ of adding 0.046g and 20.42g drying, the degassing in the 60ml bottle that is equipped with magnetic stirring bar.The red slurry that obtains was stirred 2 hours at ambient temperature, add the above-mentioned SMAO of 3.0g embodiment 1 then.Then this mixture was stirred before being used for polymerization 12 hours at ambient temperature. Embodiment 8 The preparation of two (pentamethyl-cyclopentadienyl) zirconiums of two PIVALIC ACID CRUDE (25)
Under 40 ℃, adopt to stir to two (pentamethyl-cyclopentadienyl) zirconium dichloride (0.865g, 2.001mmol) and PIVALIC ACID CRUDE (25) (0.685g, 6.710mmol) in the solution of toluene (30ml), add triethylamine (0.726g, 7.174mmol).Form white depositions immediately, by removing by filter this throw out.By under vacuum in 65 ℃ of following evaporating solvents and excessive PIVALIC ACID CRUDE (25), title compound is separated into pale powder (with 90%).According to NMR result, the title compound of preparation shows the purity greater than 98% as described. 1H NMR (toluene d 8) (s, 30H), 1.30 (s, 18H). Comparative Examples 9 The preparation of two (pentamethyl-cyclopentadienyl) zirconiums of load two PIVALIC ACID CRUDE (25)
In loft drier, in the 60ml bottle that is equipped with magnetic stirring bar, add the Kaydol oil of two (pentamethyl-cyclopentadienyl) zirconiums (0.110mmol) of 0.062g two PIVALIC ACID CRUDE (25) and 15.0g drying, the degassing.This mixture was stirred 2 hours at ambient temperature, add the above-mentioned SMAO of 2.890g embodiment 1 then.Then the slurry that obtains was stirred before being used for polymerization 12 hours at ambient temperature. Polymerization process Embodiment 10-16
In each, in sludge phase reactor, use the catalyst composition of following table 1 regulation to produce polyethylene at embodiment 10-16.
For embodiment 10-16 each, the Kaydol oil slurry of preparation one of the present invention or Comparative Examples catalyst composition.The aliquots containig of this slurry mixture is joined in 8 ounces of (250ml) bottles that comprise the 100ml hexane.Then hexene-1 (20ml) is joined in the premixed catalyst composition.Keep anhydrous condition.The polymerization time of embodiment 10-16 is 30 minutes.
Slurry-phase reactor is to be equipped with 1 liter of mechanical stirrer, stainless steel autoclave.At first by under 96 ℃, flowing down heating 40 minutes and dry reactor at drying nitrogen.After cooling reactor to 50 ℃, the 500ml hexane is joined in the reactor, add the triisobutyl aluminium (TIBA) (0.86 mole, as contaminant removal agent) of 0.25ml in hexane subsequently, and reactor component is stirred under gentle nitrogen gas stream.Under nitrogen gas stream, transfer in the reactor premixed catalyst composition and sealed reactor then.The temperature of reactor is elevated to 75 ℃ and adopt ethene to be pressurized to 150psi (1034kPa) reactor gradually.Continue heating up to the polymerization temperature that reaches 85 ℃.Unless otherwise indicated, continued polyase 13 0 minute, in this time, ethene is joined in the reactor continuously to keep constant compression force.When 30 minutes finish, with the reactor exhaust with open.
Table 1 provides the activity of embodiment 10-16, MI, FI, and MFR.As shown in table 1, catalyst composition of the present invention (embodiment 11,12,13 and 14) shows and the similar activity of Comparative Examples (embodiment 15 and 16).
Table 1
Embodiment The composition that uses Zr heap(ed) capacity (mmol) Active ?MI ?FI ?MFR
????10 ????A ????0.001 ?5714
????11 ????B ????0.001 ?91726 ?1.4 ?25.5 ?19
????12 ????C ????0.001 ?66496 ?1.2 ?22 ?18
????13 ????D ????0.001 ?14586 ?0.9
????14 ????E ????0.001 ?9624 ?1.4
????15 Comparative Examples 7 ????0.001 ?74211 ?1 ?20 ?20
????16 Comparative Examples 9 ????0.001 ?14977 ?2
Although describe and the present invention be described with reference to specific embodiment, it will be understood by those skilled in the art that the present invention guide it self to must not be in the variation of this explanation.For example, the activator of imagination load, bulky ligand and metallic compound can with one or more bulky ligand metalloscene catalysts, or traditional Z ielger-Natta or Phillips type catalyst are used together.

Claims (21)

1. a supported catalyst preparation of compositions method comprises the steps:
(a) activator of formation load; With
(b) activator of contact load and bulky ligand and metallic compound.
2. the process of claim 1 wherein with before the activator of load contacts the combination in liquid of bulky ligand and metallic compound.
3. the process of claim 1 wherein that the activator of load comprises solid support material and activator.
4. the method for claim 3, wherein activator is an aikyiaiurnirsoxan beta.
5. the process of claim 1 wherein that the activator of load is in mineral oil.
6. the method for claim 2, wherein liquid is aliphatic hydrocrbon.
7. the process of claim 1 wherein that metallic compound represented by following general formula:
ML x
Wherein M is that periodic table of elements 3-12 family's metal and L are selected from hydrogen, halogen, alkyl, alkoxide, aryl oxide, carboxylate salt, carbon diacid salt, acid amides, carbaminate and phosphide; " x " is the integer that depends on the metal valence state.
8. the process of claim 1 wherein that the activator of load is the reaction product that comprises the solid support material and the organo-aluminium compound of surface hydroxyl.
9. the process of claim 1 wherein that metallic compound is a group 4 metal compounds.
10. the method for an olefin polymerization in the presence of load catalyst system, by the activator of contact load, bulky ligand and metallic compound are produced load catalyst system.
11. the method for claim 10, wherein method is a gas phase process.
12. the method for claim 10, wherein the activator of load comprises solid support material and activator.
13. the method for claim 10, wherein metallic compound is represented by following general formula:
ML x
Wherein M is that periodic table of elements 3-12 family's metal and L are selected from hydrogen, halogen, alkyl, alkoxide, aryl oxide, carboxylate salt, carbon diacid salt, acid amides, carbaminate and phosphide; " x " is the integer that depends on the metal valence state.
14. the method for claim 10, wherein load catalyst system is in slurry state.
15. an activated olefins polymeric load catalyst system comprises bulky ligand, the activator of metallic compound and load.
16. the load catalyst system of claim 15, wherein the activator of load comprises solid support material and activator.
17. the load catalyst system of claim 15, wherein the activator of load is 99.6-80 to the weight percentage of bulky ligand and metallic compound.
18. the load catalyst system of claim 15, wherein the activator of load is the aikyiaiurnirsoxan beta of load.
19. the load catalyst system of claim 15, wherein activated olefins polymeric load catalyst system is in the liquid.
20. the load catalyst system of claim 15, wherein the activator of load is in mineral oil.
21. use the ethene polymers of the method preparation of claim 10.
CN01819398.6A 2000-10-13 2001-09-27 Method for preparing catalyst system and its use in polymerization process Expired - Fee Related CN1247618C (en)

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